Antimicrobially active substances and their production

ABSTRACT

Process for preparing antimicrobially active substances which comprises reacting alkylenebis(dithiocarbamic acid) in a salt form with a water-soluble divalent copper salt in the presence of a halogen ion under the condition that more than one molar amount of divalent copper ion to one molar amount of alkylenebis(dithiocarbamate) salt is present in the reaction system and, if desired, under the oxidative condition; optionally followed by subjecting the resulting product to oxidation. The obtained substances are advantageous in showing a stronger antimicrobial activity against a wide variety of phytopathogenic fungi and bacteria than known cupric alkylenebis(dithiocarbamate) does.

United States Patent 1 Kawano et al.

[54] ANTIMICROBIALLY ACTIVE SUBSTANCES AND THEIR PRODUCTION [75]Inventors: Toshihiko Kawano, Kyoto; Takashi Yamaoka, Kusatsu; KeiichiMaruo, Yasuhisa Furutaka, both of Osaka, all ofJapan [73] Assignee:Daikin Kogyo Company Limited,

Osaki-Fu,.lapan [22] Filed: May 1, 1970 [21] Appl. No.: 33,598

[51] Int. Cl. ..A0ln 9/12 [58] Field of Search ..260/438.1, 429 K, 429J;

[56] References Cited UNITED STATES PATENTS 1223,742 11 1953 Hester..424/286 2,845,453 7/1958 Brooks..... ...260/429 K 2,855,418 10/1958Mugnier... ..260/429 2,900,293 8/1959 Nash ...260/438.1 X

2,944,073 7/1960 Vesterman et al. ..260/438.1

3,037,041 5/1962 Couillaud ..260/438 1 3,210,394 10/1965 Nemec ctal..... ...260/438.1 X

3,379,610 4/1968 Lyon ..260/438.l X

[451 Feb. 13, 1973.

3,401,182 9/1968 Harvey et al. ..260/438.1 X

FOREIGN PATENTS 0R APPLICATIONS 1,174,844 12/1969 Great Britain..260/429 K 1,107,568 3/1968 Great Britain ..260/438.1

1,866 0/1961 Japan 2,173 0/1954 Japan OTHER PUBLICATIONS ChemicalAbstracts, Vol. 52, pg. 20863d( 1958) Chemical Abstracts, V01. 64, pg.8481e( 1966) Chemical Abstracts, Vol. 65, pg. 13962b( 1966) PrimaryExaminer-H. Sneed Attorney-Craig, Antonelli, Stewart & Hill ABSTRACTProcess for preparing antimicrobially active substances which comprisesreacting alky1enebis(dithiocarbamic acid) in a salt form with awater-soluble divalent copper salt in the presence of a halogen ionunder the condition that more than one molar amount of divalent copperion to one molar amount of alkylenebis(dithiocarbamate) salt is presentin the reaction system and, if desired, under the oxidative condition;optionally followed by subjecting the resulting product to oxidation.The obtained substances are advantageous in showing a strongerantimicrobial activity against a wide variety of phytopathogenic fungiand bacteria than known cupric alkylenebis(dithiocarbamate) does.

20 Claims, 6 Drawing Figures ANTIMICROBIALLY ACTIVE SUBSTANCES AND THEIRPRODUCTION is presently 7 NHCSS-H NHCSS-H wherein A is an alkylenegroup. As understood from this chemical formula, it is a dibasic acid.With respect to the treatment of such alkylenebis(dithiocarbamic acid)in a salt form with copper salts, it has heretofore been considered thatthe use of a monovalent copper salt gives the salt consisting ofalkylenebis(dithiocarbamate) ion and copper ion in a molar ratio of l 2or the salt consisting of alkylenebis(dithiocarbamate) ion and copperion in a molar ratio of l more than 2 depending on the employed amountof the monovalent copper salt, whereas the use of a divalent copper saltaffords only the salt consisting of alkylenebis(dithiocarbamate) ion andcopper ion in a molar ratio of l l irrespective of the employed amountof the. divalent copper salt. The above consideration comes from thefollowing facts: (1) the reaction of disodiumalkylenebis(dithiocarbamate) with an excess amount of cuprous chloridegives the salt consisting of alkylenebis(dithiocarbamate) ion and copperion in an approximate molar ratio of l 4 [Japanese Pat. Publication No.1866/1961]; (2) the reaction of disodiumalkylenebis( dithiocarbamate)with an excess amount of cupric sulfate affords the salt consisting ofalkylenebis(dithiocarbamate) ion and copper ion in an approximate molarratio of l 1 [Japanese Pat. Publikylenebis(dithiocarbamic acid) in asalt form with a water-soluble divalent copper salt in the presence of ahalogen ion under the condition that more than one molar amount ofdivalent copper ion to. one molar amount of alkylenebis(dithiocarbamate)salt is present in the reaction system affords a novel reaction producthaving alkylenebis(dithiocarbamate) moiety, divalent copper atom andhalogen atom, these being chemically bonded, in a molar ratio of l X Ywherein X and Y are respectively satisfying the following relationships:l x 3 and O Y 2. Thus, the reaction product is characteristic incontaining copper atom in a higher rate than that in the one asheretofore obtained by the use of a divalent copper salt such as cupricsulfate (i.e. cupric alkylenebis(dithiocarbamate)) and having halogenatom which is substantially not present in the latter. In addition, thereaction product gives two characteristic absorption maxima around 1580and I420 cm" in the infrared absorption spectrum, such characteristicabsorptions being not seen in known cupric alkylenebis(dithiocarbamate).Moreover, it is highly appreciable that the reaction product exhibits astrong antimicrobial activity against a wide variety of phytopathogenicfungi and bacteria. For instance, the minimum inhibitory concentrationsof the reaction product against Piricularia oryzae and Cochliobolusmiyabeanus are much lower than those of cupricalkylenebis(dithiocarbamate).

Although the copper and halogen contents in the reactionproduct arevaried with the molar ratios of copper and halogen ions toalkylenebis(dithiocarbamate) ion in the reaction system and the reactionconditions, the molar ratio of alkylenebis(dithiocarbamate) moiety,divalent copper atom and halogen atom in the reaction product is always1 X Y wherein X and Y satisfy respectively the relationships: 1 X 3 and0 Y E 2. Moreover, the reaction product has commonly the said threecharacteristics, i.e. (1) possession of copper and halogen atoms in themolecule, (2) presentation of two infrared absorption maxima around 1580and 1420 cm and (3) exertion of high antimicrobial activity.

As noted above, the product from the reaction ofalkylenebis(dithiocarbamic acid) in a salt form with a divalent coppersalt in the presence of a halogen ion under the condition that more thanone molar amount of divalent copper ion to one molar amount ofalkylenebis(dithiocarbamate) salt is present in the reaction system hasa strong antimicrobial activity and is per se useful as an antimicrobialagent. It has, however, been found that the antimicrobial activityagainst some kinds of phytopathogenic fungi and bacteria can beincreased by oxidizing the above reaction product. For instance, theexecution of the said reaction under an oxidative condition or thetreatment of the said reaction product under an oxidation conditionaffords the oxidation product, which is decreased in the copper contentbut has a somewhat higher antimicrobial activity with a reduced plantinjury in comparison with the original reaction product.

Accordingly, the basic object of the present invention is to provide thesubstance having alkylenebis(dithiocarbamate) moiety, copper atom andhalogen atom, these being chemically bonded in a molar ratio of l X Ywherein X and Y are respectively a number satisfying the relationship: 1X 3 and a number satisfying the relationship: 0 Y 2 [hereinafterreferred to as Product (I)] and its oxidation product [hereinafterreferred to as Product (")"l For preparation of the Product (I),alkylenebis(dithiocarbamic acid) in a salt form is reacted with awater-soluble divalent copper salt in the presence of a halogen ionunder the condition that more than one molar amount of divalent copperion to one molar amount of alkylenebis(dithiocarbamate) salt is presentin the reaction system.

Examples of the salt of alkylenebis(dithiocarbamic 3ethylenebis(dithiocarbamic acid), propylenebis(dithiocarbamic acid),tetramethylenebis(dithiocarbamic acid) orhexamethylenebis(dithiocarbamic acid). Among them, disodium loweralkylenebis(dithiocarbamate) (particularly disodiumethylenebis(dithiocarbamate)) is preferred because of its availabilityat a low cost.

As the water-soluble divalent copper salt, there may be exemplifiedcupric chloride, cupric bromide, cupric sulfate, cupric nitrate, etc.Examples of the source for a halogen ion are cupric chloride, cupricbromide, sodium chloride, potassium chloride, ammonium chloride, sodiumbromide, potassium bromide, sodium iodide, potassium iodide, zincchloride, manganese chloride, hydrogen chloride, hydrogen bromide,hydrogen iodide, etc. As understood from the exemplifications, cuprichalide is served not only as the copper source but also as the halogensource and, in case of using the same as the reagent, any other sourcefor a halogen ion is not required to use.

Although the amount of the source for a halogen ion is not limitative,it is favored for the production of the Product (I) having a relativelystrong antimicrobial activity to use in such an amount as can providemore than 0.1 molar amount, preferably 0.3 to 2.0 molar amount of ahalogen ion to one molar amount of alkylenebis(dithiocarbamate) salt inthe reaction system.

In carrying out the reaction, it is essential to establish such acondition that more than one molar amount of divalent copper ion to onemolar amount of alkylenebis(dithiocarbamate) salt is present in thereaction system. In case of using cupric alkylenebis(dithiocarbamate),the employment of the water-soluble divalent copper salt in any smallamount will realize such condition. On the other hand, the use of a saltof alkylenebis(dithiocarbamic acid) other than the cupric salt willrequire the employment of the water-soluble divalent copper salt in morethan 1.0 molar amount to one molar amount of the salt ofalkylenebis(dithiocarbamic acid). Although any higher amount than thesaid lower limitation may be employed, 3 molar amount of divalent copperion is the highest to be combined with one molar amount ofalkylenebis(dithiocarbamate) salt according to the present invention.Therefore, the use of the water-soluble divalent copper salt in muchexcess is of no advantage. In general, the preferred condition is to bepresent more than 1.1 molar amount, particularly L3 to 3.0 molar amountof divalent copper ion to one molar amount ofalkylenebis(dithiocarbamate) salt in the reaction system.

The reaction is normally effected in water, a watermiscible organicsolvent or their mixture. Examples of the organic solvent are methanol,ethanol, etc. From the practical viewpoint, the use of water is favored.

The temperature for reaction may be from 10 to 100 C, preferably from 30to 80C.

Since the Product (1) is substantially insoluble in water or awater-miscible organic solvent such as methanol or ethanol, its recoveryfrom the reaction mixture can be readily accomplished, for instance, bysimply filtrating.

The contents of the copper and halogen atoms in the Product (l) arevaried with the temperature and time for reaction, the concentrationsand molar ratio of alkylenebis(dithiocarbamate) ion, divalent copper ionand halogen ion, and the like.

For preparation of the Product (11), the Product (I) may be subjected tooxidation. The oxidation is carried out in a per se conventionalprocedure, for instance, by treating the Product l) with an oxidizingagent such as chlorine, bromine, chlorinated lime, oxygen, air, hydrogenperoxide or ozone in a medium such as water, a water-miscible organicsolvent or their mixture, usually at a temperature from 10 to 100 C(favorably from 30 to 80 C). In this treatment, the maintenance of thereaction system under an acidic condition, for instance, with a mineralacid such as hydrochloric acid is favored for producing the Product (11)in a higher yield.

Alternatively, the Product (11) may be produced in a single step, i.e.by carrying out the said reaction for preparation of the Product (I)under an oxidative condition. Thus, the reaction ofalkylenebis(dithiocarbamic acid) in a salt form with a water-solubledivalent copper salt in the presence of a halogen ion under thecondition that more than one molar amount of divalent copper ion to onemolar amount of alkylenebis(dithiocarbamate) salt is present in thereaction system and under an oxidative condition gives the Product (ll).in order to realize the oxidative condition, there may be employed avariety of oxidizing agents such as chlorine, bromine, chlorinated lime,oxygen, air, hydrogen peroxide or ozone, among which the use of air,i.e. aeration, is the most preferred from the economical viewpoint.Still, the maintenance of the reaction system in acid is here againfavored for the oxidation. Other reaction conditions may be decidedmaking reference to the descriptions relating to the production of theProduct (1) and of the oxidation of the same to the Product (ll).

The Product (11) is quite insoluble in water or a water-miscible organicsolvent such as methanol or ethanol and can be recovered with ease fromthe reaction mixture, for instance, by simply filtrating.

The exact chemical structures of the Product (I) and the Product (11)are not yet determined. However, it is clear that these are differentfrom any of the known copper salts of alkylenebis(dithiocarbamic acid)in the content of halogen atoms, the characteristic infrared absorptionmaxima and the strong antimicrobial activity. For instance, the saltsobtained by the reaction of disodium ethylenebis(dithiocarbamate) withcupric chloride in a molar ratio of l 2 (cf. Example (44), the reactionof disodium ethylenebis(dithiocarbamate) with cupric sulfate in a molarratio of 1 2 in the presence of sodium chloride (cf. Example 1 l thereaction of the product, obtained by reacting disodiumethylenebis(dithiocarbamate) with cupric chloride in a molar ratio of 12, with chlorinated lime (cf. Examples 19 and 20) and the reaction ofdisodium ethylenebis(dithiocarbamate) with cupric sulfate in a molarratio of 1 2 in the presence of sodium chloride while aeration (cf.Example 31) give the characteristic infrared absorption maxima at 1580and 1420 cm" as shown in FIGS. 3, 4, 5 and 6 of the accompanyingdrawings, whereas the salts obtained by the reaction of disodiumethylenebis(dithiocarbamate) with cupric sulfate in a molar ratio of l 3and the reaction of disodium ethylenebis(dithiocarbamate) with cupricchloride in a molar ratio of 3 2.5 have no such characteristicabsorption maxima as shown in FIGS. 1 and 2 of the accompanyingdrawings.

As stated above, the Product (I) and the Product (11) exhibit strongantimicrobial activities, especially against a wide variety ofphytopathogenic fungi. It is particularly notable that, compared withthe known metal salts of alkylenebis(dithiocarbamic acid), the Product(I) and the Product (11) are much more stable and show a high andprolonged or residual activity in controlling various fungus infectionsin rice plants. Advantageously, they produce no material plant injury inthe practical use. Moreover, they show very low toxicity against warmblooded animals and fishes and are of high safety to human beings.Therefore, they are useful for controlling plant diseases caused byphytopathogenic fungi and bacteria including diseases in rice plants(e.g. blast, Helmintosporium leaf spot, sheath blight, stem rot),diseases in cucumbers (e.g. downy mildew, anthracnose, powdery mildew),diseases in tomatoes (e.g. late blight, leaf mold, early blight, graymold), diseases in egg plants (e.g. phytophthora rot), diseases inonions (e.g. Alteraria leaf spot), diseases in strawberries (e.g. graymold), diseases in apples (e.g. Alternaria leaf spot), diseases in pears(e.g. black spot), diseases in citrus (e.g. canker), diseases in grapes(e.g. powdery mildew), etc. In comparison of these two products, theProduct (11) is generally and somewhat superior to the Product (I) inthe antimicrobial activity and the plant injury, although both are useful as antimicrobial agents. Still, they can product the reduction ofmite populations on plants.

The Product (I) and the Product (11) may be applied as such, but theyare usually admixed with an appropriate carrier material(s) to make sucha preparation form(s) conventionally employed for agricultural chemicalsas dust and wettable powder. The most economical carrier material iswater, and their aqueous suspension may be practically and widely used.Other examples of the carrier material are clay, talc, kaolin,bentonite, sericite, etc. Various surfactants or wetting agents may beincorporated into such compositions. Moreover, any other agriculturalchemicals such as herbicides, insecticides, fungicides, plant growthregulators and fertilizers may be also incorporated therein.

Practical and presently preferred embodiments of the present inventionare illustratively shown in the following Examples wherein parts andpercent are by weight.

EXAMPLE 1 To a solution of 10.9 (0.03 mol) ofNaSSCI-INCI-hCl-h-NHCSSNa-6H2O in 150 ml of water, a solution of 6.7 g(0.039 mol) of CuCl -2l-l O in 150 ml of water is added at 30 C. After 3hours, the reaction mixture is filtered. The collected substance iswashed with water to remove free copper and chlorine ions and dried togive brown solid (8.8 g).

Elementary analysis: Cu, 27.4 percent; Cl, 5.77 percent. Characteristicinfrared absorption maxima: 1580, 1420 cm. Decomposing point: 162 167 C.

EXAMPLE 2 To a solution of 10.9 g (0.03 mol) ofNaSSCHNCPhCI-h-NHCSSNa-61-120in150 m1 of water, a solution 'of 7.7 g(0.045 mol) of CuCl -2H O in cent. Characteristic infrared absorptionmaxima: 1580, 1420 cm. Decomposing point: 158 162 C.

EXAMPLE 3 To a solution of 10.9 g (0.03 mol) of NaSSCHNCH -CH NHCSSNa-6HO in 10 m1 of water, a solution of 14.4 g (0.052 mol) of ZnSO -7H O inml of water is added at 20 C. After 2 hours, the reaction mixture isfiltered. The collected substance is washed with water and suspended inml of water. To the suspension, a solution of 15.3 g (0.09 mol) of CuCl-2H O in 150 ml of water is added at 30 C. After 2 hours, the mixture isfiltered. The collected substance is washed with water and dried to givebrown solid (10.1 g)

Elementary analysis: Cu, 32.9 CI, 9.2 Characteristic infrared absorptionmaxima: 1580, 1420 cm". Decomposing point: 153 160 C.

EXAMPLE 4 ing point: 200 205 C.

EXAMPLES To a solution of 10.9 g (0.03 mol) of NaSSCHNCH- CH NHCSSNa-6HO in 100 ml of water, a solution of 3.5 g (0.065 mol) of NH CI in 50 mlof water is added. Then, a solution of 8.7 g (0.05 mol) of CuCl,-2H O in150 ml of water is added thereto at 50 C. After 4 hours, the reactionmixture is filtered.

The collected substance is washed with water and dried to give brownsolid 10.0 g).

Elementary analysis: Cu, 31.4 CI, 9.3 Characteristic infrared absorptionmaxima: 1580, 1420 cm". Decomposing point: 162 C.

EXAMPLE 6 To a solution of 13.5 g (0.06 mol) of CuBr in 150 ml of water,a solution of 10.9 g (0.03 mol) of NaSSCI-INCH CI-h-NHCSSNa-6H O in 130m1 of water is added with stirring at 25 C. After 5 hours, the reactionmixture is filtered. The collected substance is washed with water anddried to give yellowish brown solid (10.5 g).

Elementary analysis: Cu, 28.9 Br, 14.2 Characteristic infraredabsorption maxima: 1580, 1420 cm".

' Decomposing point: 162 166 C.

EXAMPLE 7 To a mixture of 7.4 g of propylenediamine, 8 g of sodiumhydroxide and 50 g of water, 15.2 g of carbon disulfide are added toproduce NassCHNCll ClflCl-l )NHCSSNa (0.1 mol). The resultant mixture isdiluted with water to make 500 ml, neutralized and warmed to 40 C. Tothe mixture, a solution of 34 g (0.2 mol) of CuCl -21-l O in 400 ml ofwater is added under stirring. After 3 hours, the reaction mixture isfiltered. The collected substance is washed with water and dried to giveyellowish brown solid (33 g).

Elementary analysis: Cu, 29.1 C1, 7.2 Decomposing point: 159 163 C.

EXAMPLE 8 To a solution of- 15.6 g (0.05 mol) of NaSSCl-lN(C1-l -NHCSSNain 200 ml of water, a solution of 17 g (0.1 mol) of CuCl .2H O in 200 mlof water is added at 80 C. After hours, the reaction mixture isfiltered. The collected substance is washed with water and dried to giveyellowish brown solid (18 g).

Elementary analysis: Cu, 27.4 Cl, 8.71 Decom-. posing point: 157 -163 C.

EXAMPLE 9 To a solution of 21.8 g (0.06 mol) ofNaSSCHNCl-bCl-h-NHCSSNa61-120 and 7 g (0.12mo1) of l-laCl in 250 ml ofwater, a solution of 19.5 g (0.078 mol) of CuSO4 -5I- l in 2 50 mlofwater is added at 60 C. After 5 hours, the reaction mixture is filtered.The collected substance is washed with water and dried to give brownsolid (17 g).

Elementary analysis: Cu, 28.1 Cl, 4.8 Characteristic infrared absorptionmaxima: 1580, 1420 cm". Decomposing point: 155 160 C.

EXAMPLE To a solution of 21.8 g (0.06 mol) ofNaSSCl-lNcl-lzCHz-NHCSSNa'61-1 0 and 7 g (0.12 mol) of NaCl in 250 m1 ofwater, a solution of 27.5 g (0.11 mol) of CuSOl 61-120 in 250 ml ofwater is added at 30 C. After 3 hours, the reaction mixture is filtered.The collected substance is washed with water and dried to give brownsolid (19 g).

Elementary analysis: Cu, 32.7 CI, 8.4 Characteristic infrared absorptionmaxima: 1580, 1420 cm".

Decomposing point: 165 170 C.

EXAMPLEII To a solution of 21.8 (0.06 -mol) ofNaSSCHNCI-hClh-NHCSSNa-6H2O and 7.6 g (0.13 mol) of NaCl in 250 ml ofwater, a solution of 31.6 g (0.126 mol) of CuSO -5H2O in 250 ml of wateris added at 60 C. After 5 hours, the reaction 250 ml of water, asolution of 31.5 g (0.125 mol) of CuSO,'5H O in 250 ml of water is addedat 60 C. After 5 hours, the reaction mixture is filtered. The collectedsubstance is washed with water and dried to give yellowish brown solid(23 g).

Elementary analysis: Cu, 27.8 Br, 21.4 Characteristic infraredabsorption maxima: 1580, 1420 cm". Decomposing point: 188 193 C.

EXAMPLE 13 EXAMPLE 14 To a solution of 21.8 g (0.06 mol) ofNaSSCHNCH2CHz-NHCSSNa-6H2O and 1.8 g (0.03 mol) of NaCl in 250 ml ofwater, a solution of 31.6 g (0.126 mol) of CuSO4-5H2O in 250 ml of wateris added at 60 C. After 5 hours, the reaction mixture is filtered. Thecollected substance is washed with water and dried to give brown solid(17.5 g).

Elementary analysis: Cu, 31.7 Cl, 5.7 Characteristic infrared absorptionmaxima: 1580, 1420 cm". Decomposing point: 157162 C.

EXAMPLE 15 To a solution of 21.8 g (0.06 mol) of NaSSCHNCl-l-CH2Nl-1CSSNa-6H2O and 9.6 g (0.18 mol) of NH Cl in 250 ml of water, asolution of 36.5 g (0.15 mol) of Cu(NO H O in 250 ml of water is addedat 60 C. After 5 hours, the reaction mixture is filtered. The collectedsubstance is washed with water and dried to give greenish brown solid(20.5 g).

Elementary analysis: Cu, 28.9 C1, 12.7 Characteristic infraredabsorption maxima: 1580, 1420 cm". Decomposing point: 200 205 C.

EXAMPLE 16 To a solution of 21.8 g (0.06 mol) ofNaSSCHNCI-hCl-h-NHCSSNa-6H O in 290 ml of water, a solution of 31.5 g(0.125 mol) of CuSO 51 1 0 in 250 m1 of water is added at 30 C, and then6 g (0.058 mol) of cone. hydrochloric acid are'added thereto. After 5hours, the reaction mixture is filtered; The collected substance iswashed with water and dried to give brown solid (18 g).

Elementary analysis: Cu, 31.4 Cl, 8.7 Characteristic infrared absorptionmaxima: 1580, 1420 cm". Decomposing point: 151- 154 C.

EXAMPLE 17 To a mixture of 7.4 g of 1 ,2-propylenediamine, 8 g of sodiumhydroxide and 50 g of water, 15.2 g of carbon disulfide are added toproduce NaSSCHNCH C1-1(CH )NHCSSNa (0.1 mol). The resulting mixture isdiluted with 500 ml of water, neutralized and 11.8 g (0.2 mol) of sodiumchloride are dissolved therein. The resultant solution is warmed to 50C, and a solution of 50 g (0.2 mol) of CuSO '5H O in 400 ml of water isadded thereto. After 5 hours, the reaction mixture is filtered. Thecollected substance is washed with water and dried to give yellowishbrown solid (31.5 g).

Elementary analysis: Cu, 28.8 C1, 9.4 Decomposing point: 178 -183 C.

EXAMPLE 18 To a mixture of 11.6 of hexamethylenediamine, 8 g of sodiumhydroxide and 60 g of water, 15.2 g of car-' bon disulfide are added toproduce NaSSCHN(CH NHCSSNa (0.1 mol). The resulting mixture is dilutedwith 500 ml of water, neutralized and 1 1.8 g (0.2 mol) of sodiumchloride are dissolved therein. The resultant solution is warmed to 40C, and a solution 50 g (0.2 mol) of CuSO 5H O in 500 ml of water isadded thereto. After 5 hours, the reaction mixture is filtered. Thecollected substance is washed with water and dried to give yellowishbrown solid (34 g). v

Elementary analysis: Cu, 27.8 Cl, 8.2 Decomposing point: 160 163 C.

EXAMPLE 19 To a mixture of 36.4 g (0.1 mol) of NaSSCHNCH CH -NHCSSNa61-1 in 350 ml of water, a solution of 34.1 g (0.2 mol) of CuCl: 21120in 350 ml of water is added at 60 C. After hours, the reaction mixtureis filtered. The collected substance is washed with water and dried togive greenish brown solid (34 g).

Elementary analysis: Cu, 32.7 Cl, 11.45 Decomposing point: 205 210 C.

EXAMPLE 20 The solid product g) obtained in Example 19 is pulverized ina mortar and suspended in 250 ml of water. To the suspension, 97 g ofconc. hydrochloric acid are added, and then 16 g of chlorinated lime areadded thereto at 50 C in about 30 minutes. After 30 minutes, thereaction mixture is filtered. The collected substance is washed withwater and dried to give yellowish brown solid (4.8 g).

Elementary analysis: Cu, 20.86 Cl, 11.43 Characteristic infraredabsorption maxima: 1580, 1420 cm". (cf. FIG. 5 of the accompanyingdrawings). Decomposing point: 200 205 C.

EXAMPLE 21 The solid product (10 g) obtained in Example 19 is pulverizedin a mortar and suspended in 100 ml of water. After warming to 40 C, 7 gof chlorine gas are introduced into the suspension. After 1 hour, thereaction mixture is filtered. The collected substance is washed withwater and dried to give yellowish brown solid (3.5 g).

Elementary analysis: Cu, 21.24 Cl, 10.97 Decomposing point: 175 180C.

EXAMPLE 22 The solid product (10 g) obtained in Example 19 is pulverizedin a mortar and suspended in 100 ml of water. After warming to 30 C, 10g of bromine are added thereto. The resultant mixture is then stirredfor 1 hour. The reaction mixture is filtered. The collected substance iswashed with water and dried to give yellowish brown solid (6.5 g).

Elementary analysis: Cu, 22.13 Cl, 11.43 Decomposing point: 195 205 C.

EXAMPLE 23 To a solution of 21.8 g (0.06 mol) ofNflSSCHNCH-zCHzNHCSSNfi6H2O in 250 ml of water, a solution 22.5 g (0.132mol) of CuCl '2H O in 250 ml of water is added at 60 C. After 5 hours,the resultant mixture is cooled to 50 C, and 200 g of conc. hydrochloricacid are added thereto. To the resulting mixture, 35 g of chlorinatedlime are added. After 1 hour, the reaction mixture is filtered. Thecollected substance is washed with water and dried to give yellowishbrown solid (13 g).

Elementary analysis: Cu, 20.24 Cl, 11.77

Decomposing point: 205 -210 C.

' EXAMPLE 24 To a solution of 21.8 (0.06 mol) ofNaSSCHNCI-bCl-h-NHCSSNa-61-120 in 250 ml of water, a solution of 27.0 g(0.12 mol) of CuBr in 250 ml of water is added at C. After Sliours, g ofconc. hydrochloric acid are added thereto, and then 35 g of chlorinatedlime are added. After 1 hour, the reaction mixture is filtered. Thecollected substance is washed with water and dried to give yellowishbrown solid (14.5 g).

Elementary analysis: Cu, 18.14 Br, 22.71 Decomposing point: C.

EXAMPLE 25 EXAMPLE 26 To a solution of 36.4 g (0.1 mol) of NaSSCl-lNCl-l-CH NHCSSNa-6H O in 350 ml of water, a solution of. 37.5 g (0.22 mol) ofCuCl -2H O in 350 ml of water is added at 60 C. Then, 40 g of conc.hydro- ,chloric acid are added, and air is introduced therein at a rateof 2 liters per minute for 5 hours. The

reaction mixture is filtered. The collected substance is washed withwater and dried to give yellowish brown solid (25.5 g).

Elementary analysis: Cu, 21.43 Cl, 11.31 Decomposing point: 207 212 C.

EXAMPLE 27 To a solution of 7.4 g of 1,2-propylenediamine in 20 ml ofwater, 15.2 g of carbon disulfide are added, and a solution of 8 g ofsodium hydroxide in 20 ml of water is added thereto to produceNaSSCHNCH,CH(CH )Nl-lCSSNa (0.1 mol). The resultant solution is dilutedwith water to make 350 ml, and a solution of 34.1 g

(0.2 mol) of CuCl,-2H,O in 350 ml of water is added thereto at 70 C.After hours, the resulting mixture is cooled to 50 C, 200 g of cone.hydrochloric acid are added thereto, and then 30 g of chlorinated limeare added. After 1 hour, the reaction mixture is filtered. The collectedsubstance is washed with water and dried to give yellowish brown solid(21 g).

Elementary analysis: Cu, 19.83 Cl, 10.74 Decomposing point: l67 173C.

EXAMPLE 28 To a solution of 1 1.6 g of hexamethylenediamine in 30 ml ofwater, 15.2 g of carbon disulfide are added, and a solution of 8 gsodium hydroxide in 30 ml of water is added to produce NaSSCHN(CHNHCSSNa (0.1 mol). The resultant solution is diluted with water to make400 ml, and a solution of 37.5 g (0.22 mol) of CuC1 '2l-1 O in 350 ml ofwater is added at 60 C. After 5 hours, 180 g of cone. hydrochloric acidare added, and then 30 g of chlorinated lime are added thereto. After 1hour, the reaction mixture is filtered. The collected substance iswashed with water and dried to give yellowish brown solid (23 g).

Elementary analysis: Cu, 17.82 Cl, 9.57

A Decomposing point: 158 162 C.

EXAMPLE 29 To a solution of 36.4 g (0.1 mol) ofNaSSCHNCl'hCI-h-NHCSSNa'6H O and 11.7 g (0.2 mol) of NaCl in 350 ml ofwater, a solution of 52.5 g (0.21 mol) of CuSO -5I-l O in 400 ml ofwater is added at 60 C. After 5 hours, the precipitate is collected byfiltration, washed with water and dried to give greenish brown solid(34.5 g).

Elementary analysis: Cu, 32.44%; Cl, 11.81 Decomposing point: 200 205 C.

EXAMPLE 30 The solid product g) obtained in Example 29 is pulverized ina mortar and suspended in 250 ml of water. To the suspension, 97 g ofcone. hydrochloric acid are added, and then 16 g of chlorinated lime areEXAMPLE 31 To a solution of 21.8 g (0.06 mol) of NaSSCHNCHZCHNHCSSNa-6H2O and 7.6 g (0.13 mol) of NaCl in 250 ml of 0,0-Dethyl-Sbenxylthiophosphate water, a solution of 31.6 g

(0.126 mol) of CuSO -5H2O in 250 ml of water is added at 60 C. Then, 30g of cone. hydrochloric acid are added thereto. Air is introducedtherein at a rate of 1 liter per minute for 5 hours. The reaction isfiltered. The collected substance is washed with water and dried to giveyellowish brown solid (15 g).

Elementary analysis: Cu, 20.49 Cl, 11.07 Characteristic infraredabsorption maxima: 1580, 1 420 cm (cf. FIG. 6 of the accompanyingdrawings). Decomposing point: 205 210 C.

EXAMPLE 32 l n ,,...(9.-.Q6 2 -9 NaSSCHNCl-lzCH2 Nl-lCSSNa-6H2O and 18 g(0.15 mol) of KBr in 250 ml of water, a solution of 31.5 g (0.126 mol)of CuSO4-5H O in 250 ml of water is added. After addition of 30 g ofcone. hydrochloric acid, air is introduced therein at a rate of 1 literper minute for 5 hours. The reaction mixture is filtered. The collectedsubstance is washed with water and dried to give yellowish brown solid(20 g).

Elementary analysis: Cu, 18.21 Br, 22.15 Decomposing point: 185 l C.

REFERENCE EXAMPLE To a solution of 10.9 g (0.03 mol) of NaSSCHNCI-ICHZ-NHCSSNa-6H2O in ml of water, a solution of 4.3 g (0.025 mol) of CuCl-2H2O in 100 ml of water is added at room temperature. After 5 hours,the reaction mixture is filtered. The collected substance is washed withwater to give dark brown solid (6.7 g).

Elementary analysis: Cu, 23.9 Cl, 0.4 No infrared absorption maxima at1580 and 1420 cm (cf. P16. 2 of the accompanying drawings).

EXAMPLE A Parts Product in Example 1 25 Kaolin 60 Sodium alkylsulfate 10Sodium ligninsulfonate 5 The above materials are mixed uniformly to makea wettable powder preparation.

EXAMPLE B Pans Product in Example 22 25 Kaolin 60 Sodium alkylsulfate 10Sodium ligninsulfonate S The above materials are mixed uniformly to makea wettabl'e powder preparation.

EXAMPLE C Parts Product in Example 2 S Kaolin 90 Sodium alkylsulfate 5The above materials are mixed uniformly to make a dust preparation.

EXAM PLE D Parts Product in Example 14 5 Kaolin 90 Sodium alkylsulfate 5The above materials are mixed well to make a dust preparation.

EXAMPLE E Parts Product in Example 25 S Kaolin 90 Sodium alkylsulfateThe above materials are mixed uniformly to make a dust preparation.

Some of the test results which support the excellent antimicrobialactivity of the Product (I) and the Product (2) are shown below,compared with some copper salts of alkylenebis(dithiocarbamic acid)prepared by conventional procedures and some known antimicrobial agents.

TEST 1 In a test tube of 1 cm in diameter and cm in length, 1 ml of anaqueous suspension of the test compound was charged, and 1 ml of a sporesuspension of Piricularia oryzae or Cochliobolus miyabeanus was addedthereto. After shaking well, 0.3 ml of the mixture was pipetted anddropped on a glass plate. The plate was kept in a wet room at 28 C for24 hours. The germination situation of the spores on the plate was thenobserved under a 150 fold microscope to determine the minimum inhibitoryconcentration of the test compound against germination (i.e. the minimumconcentration of the test compound producing 100 percent inhibition ofgermination).

The results are shown in Table 1.

") The numeral corresponds to the number of each Example. The product inReference Example is the product from the reaction etween disodiumethylenebis(dithiocarbamate) and cupric chloride in a molar ratio of 32.5. The cuprous complex salt is the product from the reaction betweendisodium ethy1enebis(dithiocarbamate) and cuprous chloride in a molarratio of 1:4.

TEST 2 In the same manner as in Test 1, the minimum inhibitoryconcentrations of some test compounds against the germination of thespores of Piricularia oryzae and Cochliobolus miyabeanus weredetermined.

The results are shown in Table 2.

Prevention value (75) TABLE 2 Test compound Minimum inhibitoryConcentration (vlmll Piricularia Cochliobolus oryzae miyabeanus 9 10.010.0 10 5.0 10.0 11 1.0 2.5 12 1.0 2.5 13 5.0 20.0 14 2.5 5.0 15 1.0 2.516 10.0 10.0 17 2.5 10.0 18 5.0 10.0 Cupric ethylenebis-(dithiocarbamate) 25 50 Pentachlorobenzyl alcohol0,0-Diethyl-S-benzylthiophosphate 25 See the remarks under Table 1.

TEST 3 In the same manner as in Test 1, the minimum inhibitoryconcentrations of some test compounds against the germination of thespores of Piricularia oryzae and Cochliobolus miyabeanus weredetermined.

The results are shown in Table 3.

) See the remarks under Table 1.

TEST 4 The test compound in wettable powder form was diluted with waterto a designed concentration and applied to rice plants of fourth-leafstage cultured in pots. After drying in air, a spore suspension ofPiricularia oryzae or Cochlibolus miyabeanus was sprayed thereon. On the4th day after spraying, the number of infectious spots per plant wascounted, and the prevention value was calculated according to thefollowing equation:

"'Heri 55583iiflfctiuiii the Average number of infectious spots perplant in the treated plot Average number of infectious spots per plantin the untreated plot In the same manner as in Test 4, the preventionvalues of some test compounds against infection with Piricularia oryzaeand Cochliobolus miyabeanus were determined.

The results are shown in Table 5.

The results are shown in Table 4.

TABLE 4 Test Con Piricularia Cochliobolus compound centoryzae miyabeanusra Average Preven- Average Prvention number tion number tion (ppm) ofinvalue of invalue fectious (91 fectious spots per spots per plant plant1 300 10.32 69.5 18.52 69.2 2 300 9.87 70.8 17.31 71.2 3 300 6.42 81.012.44 79.4 4 300 6.23 81.6 11.22 81.4 5 300 9.21 72.8 14.37 76.1 6 3008.42 75.1 13.23 78.0 7 300 9.33 72.4 13.33 77.8 8 300 7.43 78.0 1 1.8180.4 Product in I Reference 300 17.88 47.1 3 3.62 43.7 7 Example Cuprouscomplex 300 1 5.43 54.4 38.41 36.1 salt Pentachlorobenzyl 500 9.74 71.227.44 54.4 alcohol 0,0-Diethyl- S-benzylthio- 500 12.0 64.5 16.13 73.2phosphate 1 Untreated 33 .78 60.12

*) See the remarks under Table 1.

TEST 5 TABLE 5 Test Con- Piricularia Cochliobolus compound centoryzaemiyabeanus ra- Average Preven- Average Prevention number tion numbertion (ppm) of invalue of invalue fectious fectious. (17) spots per spotsper plant plant 9 300 12.53 67.4 19.05 65.2 10 300 10.03 73.9 16.80 69.311 300 6.03 84.3 9.19 83.2 12 300 7.22 81.2 10.73 80.4 13 300 11.26 70.715.16 72.3 14 300 8.15 78.8 14.01 74.4 15 300 6.84 82.2 9.91 81.9 16 30012.22 68.2 18.94 65.4 17 300 9.87 74.3 13.41 75.5 l8 300 9.53 75.2 14.5673.4 Cupric eth lene- 300 21.40 44.3 31.31 42.8 bis dithiocarbamate)Pentachlorobenzyl 500 10.33 73.1 22.77 58.4 alcohol Y 0,0-Diethyl-S-benzylthro- S 1 1.83 69.2 12.75 76.7 pjhosphate ntreated 38.42 54.73

) See the remarks under Table 1.

determined.

TEST 6 The results are shown in Table 6.

TABLE 6 Test Con- Piricularia Cochliobolus compound centoryzaemiyabeanus ra- Average Preven- Average Prevention number tion numbertion (ppm) of invalue of invalue fectious (91:) fectious (5) spots perspots per plant plant l 300 10.4 70.8 19.2 68.7 2 300 10.0 71.4 18 .470.0 4 300 7.2 79.3 12.0 80.4 5 300 9.8 72.0 15.4 74.6 10 300 10.9 68.817.1 72.0 12 300 7.4 79.0 11.3 81.7 15 300 7.2 79.3 10.1 83.2 16 30014.2 59.6 19.3 68.5 20 300 6.5 80.8 15.0 75.5 23 300 6.3 82.0 9.4 84.624 300 5.8 83.3 9.0 85.2 26 300 6.2 82.2 9.7 84.2 2 30 300 7.1 79.5 16.772.8 31 300 6.8 80.5 10.4 83.0 32 300 7.3 79.1 9.6 84.7 0,0-Diethyl-S-benzylthio 500 14.2 59.6 17.0 72.2 phosphate Pentachlorobenzyl 50010.0 71.4 28.2 54.0

alcohol Product in Reference 300 18.0 48.5 34.5 43.4 Example Cupricethylene- 300 18.0 48.5 32.4 46.8 bis(dithio carbamate) Cuprous complex300 16.0 54.2 39.3 35.5 salt Untreated 35.0 60.8

35 See the remarks under Table 1.

TEST 7 The test compound in wettable powder form was diluted with waterto make a designed concentration and applied to the onions grown in thefield of 2.8 m per plot in four replicates per each concentration once aweek at a rate of 100 to 300 liters per 10 a for 3 weeks. Then, theinfection of the onions with Alternaria porri was observed to determinethe number of infectious spots and calculate the rate of diseased leavesaccording to the following equation:

Rate of diseased leaves Number of diseased leaves X ethylenebis(di- I7500.20 9.5 3 Serious infection thiocarbamate) Untreated 0.33 l6.2

The results are shown in Table 9. See the remarks under Table l.

TABLE 9 TEST 8 Test compound Concen- Rate of lndexof The test compoundin wettable powder form was tration diseased infectlon diluted withwater to make I000 ppm concentration (ppm) leaves and applied to theonions grown in the field of 1.2 m X 2.3 m per plot in three replicatesper each test comggg 34% pound once a week at a rate of 100 to 300liters per 10 14 500 1 1 a for 7 weeks. Then, the infection of theonions with Al- 1000 33-; 8-32 ternaria porri was observed to determinethe number of 33% infectious spots per leaf. Manganese The results areshown in Table 8. elllyleneblsw" thiocarbamate) 48 5 o 63 U t t d TABLE3 Test compound Concentration No. of infectious (ppm) per leaf See theremarks under Table l.

1 1000 0.63 TEST 10 4 1000 0.35 7 1000 0.43 The test compound inwettable powder form was {38% 8-32 diluted with water to make 1000 ppmconcentration 12 1000 0140 and applied to the cucumbers grown in thefield of 1 m 14 (159 X 1.8 m per plot once a week at a rate of 280liters per 17 1000 0.46 10 f h b 20 1000 038 a for 6 weeks. Then, theinfection 0 t e cucum ers g; 1 1888 8.2.? with Sphaerotheca fuligineawas observed to determine 26 000 30 the index of infection according tothe following equa 30 1000 0.46 tron: 7 7 V 7 H W EInfection gradeXNumber of leaves in the infection grade Index of Infection:

Total number of tested leaves 31 1000 V 7 wherein the infection grade isbased on the following 32 1000 0.42 35 Manganese cntena. ethylenebis-1000 0.68 (dithiocarbamaw) Grade Rate of infectious area (96) Product inReference 1000 0.98 0 0 Example 1 0 to 30 Cupric 40 2 30 to 60ethylenebls- I000 1.21 3 60 m 100 (drthiocarbamate) Cuprous 1000 0.83""P The results are shown in Table 10. Untreated 1.55

TABLE 10 See the remarks under Table l.

Test compound Concentration No. of infectious TEST 9 (ppm) spots perleaf The test compound in wettable powder form was 1 I000 048 dilutedwith water to make a designed concentration 4 1000 0.28 and applied tothe cucumbers grown in the field of 3.7 g :838 83? m per plot in threereplicates per each concentration 11 1000 0.40 once a week at a rate of100 to 300 liters per 10 a for 3 :3 188g 82? weeks. Then, the infectionof the cucumbers with Pseu- 17 1000 p doperonospora cubensis wasobserved to determine the 20 1000 010 rate of diseased leaves as in Test8 and calculate the g {888 8:}: index of infection according to thefollowing equation: 26 1000 0.13

Index of zllnfeetlon gradeX Number of leaves 1n the infection gradeTotal number of tested leaves wherein the infection grade is based onthe following 30 1000 0.12 criteria. 31 1000 0.15 32 1000 0.20

Manganese Grade Observation ethylenebis- 1000 0.55

(dithiocarbamate) Product in 0 No infection Reference 1000 0.88 1 Slightinfection Example 2 Medium infection Cupric ethylenebis- 1000 0.93dithiocarbam ate) Cuprous 1000 0.90 complex salt Untreated 0.95

*) See the remarks under Table 1.

TEST 1 1 The test compound in wettable powder form was diluted withwater to make 1000 ppm concentration and applied to the pear trees grownin the field once a weekat a rate of 110 liters per 10 a for weeks.Then, the infection of the pear trees with Alternaria kikuchiana wasobserved on 250. leaves to determine the number of infectious spots perleaf. The plant injury was also determined by observing russets in thefollowing criteria:

Russets Plant injury None Less than of small immature fruits l0 or moreof small immature fruits TABLE 1 1 Test compound Concen- InfectiousPlant tration spots per injury (pp f 3 1000 7.5 t 4 1000 6.0 i 6 10006.9 i 8 1000 8.3 i 9 1000 9.8 i 1 l 1000 6.3 i 13 1000 7.3 i: 18 100010.5 1 20 1000 7.8 21 1000 10.1 23 1000 8.9 26 1000 8.4 28 1000 9.8 301000 -7.3 31 1000 8.1 V Zinc dimethyldithiocarbamate, 50

1000 l 1.2 Bis(dimethyldicarbamo yl) ethylenedia.mine, 30 Product inReference Example 1000 29.5 i Cupric ethylenebis- 1000 28.2 i(dithiocarbamate) cuprous complex salt 1000 20.2 Untreated 38.5

") See the remarks under Table 1.

What is claimed is:

1. A process for preparing fungicidally and bactericidally activesubstances which comprises reacting a1 kylenebis(dithiocarbamic acid) ina salt form with a water-soluble divalent copper salt in the presence ofa halogen ion under the condition that more than one molar amount ofdivalent copper ion to one molar amount of alkylenebis(dithiocarbamate)salt is present in the reaction system. a

2. The process according to claim 1, wherein the reaction is carried outin water, a water-miscible organicsolvent or their mixture.

3. The process according to claim 1, wherein the product is recoveredfrom the reaction mixture.

4. The process according to claim 1, wherein the reaction is carried outin the presence of more than 0.1 molar amount of a halogen ion to onemolar amount of alkylenebis(dithiocarbamate) salt under the conditionthat more than 1.1 molar amount of divalent copper ion to one molaramount of alkylenebis(dithiocarbamate) salt is present in the reactionsystem.

5. The process according to claim 1, wherein the reaction is carried outin the presence of 0.3 to 2.0 molar amount of a halogen ion to one molaramount of alkylenebis(dithiocarbamate) salt under the condition that 1.3to 3.0 molar amount of divalent copper ,ion to one molar amount ofalkylenebis(dithiocarbamate) salt is present in the reaction system.

6. The process according to claim 1, wherein the reaction is carried outat a temperature from 10 to C.

7. The process according to claim 1, wherein the reaction is carried outwith cupric halide.

8. The process according to claim 1, wherein the reaction is carried outwith a water-soluble divalent copper salt other than cupric halide inthe presence of a halogen ion.

9. The process according to claim 1, wherein the reaction is carried outunder an oxidative condition.

10. The process according to claim 9, wherein the reaction is carriedout under aeration.

11. The process according to claim 9, wherein the reaction is carriedout under an acidic condition.

12. The process according to claim 9, wherein the reaction is carriedout in the presence of 0.3 to 2.0

molar amount of a halogen ion to one molar amount ofa1kylenebis(dithiocarbamate) salt under the condition that 1.3 to 3.0molar amount of divalent copper ion to one molar amount ofa1kylenebis(dithiocarbamate) salt is present in the reaction system.

13. The process according to claim 9, wherein the reaction is carriedout at a temperature from 10 to 100 C.

14. The process according to claim 1, followed by treatment of thereaction product with an oxidizing agent.

15. The process according to claim 14, wherein the reaction is carriedout under an acidic condition.

16. The process according to claim 14, wherein the treatment is carriedout at a temperature from 10 to 100 C.

17. An fungicidally and bactericidally active substance havingalkylenebis(dithiocarbamate) moiety, divalent copper atom and a halogenatom, these being chemically bonded, in a molar ratio of l X Y wherein Xand Y are respectively satisfying the following relationships: l X 3 and0 Y 2, which is obtained by reacting alkylenebis(dithiocarbamic acid) ina salt form with a water-soluble divalent copper salt in the presence ofmore than 0.1 molar amount of a halogen ion to one molar amount ofalkylenebis(dithiocarbamate) salt in an aqueous medium at a temperaturefrom 10 to 100 C under the condition that more than 1.1 molar amount ofdivalent copper ion to one molar amount of alkylenebis(dithiocarbamate)salt is present in the reaction system, and recovering the precipitatefrom the reaction mixture.

18. A composition for agricultural use containing the stance whichcomprises the oxidation product of the fungicidally and bactericidallyactive substance of substance according to claim 17. claim 17 and aninert carrier. 20. A composition for agricultural use containing the 19.A fungicidally and bactericidally active subactive substance of claim 19and an inert carrier.

a: a: a:

1. A process for preparing fungicidally and bactericidally activesubstances which comprises reacting alkylenebis(dithiocarbamic acid) ina salt form with a water-soluble divalent copper salt in the presence ofa halogen ion under the condition that more than one molar amount ofdivalent copper ion to one molar amount of alkylenebis(dithiocarbamate)salt is present in the reaction system.
 2. The process according toclaim 1, wherein the reaction is carried out in water, a water-miscibleorganic solvent or their mixture.
 3. The process according to claim 1,wherein the product is recovered from the reaction mixture.
 4. Theprocess according to claim 1, wherein the reaction is carried out in thepresence of more than 0.1 molar amount of a halogen ion to one molaramount of alkylenebis(dithiocarbamate) salt under the condition thatmore than 1.1 molar amount of divalent copper ion to one molar amount ofalkylenebis(dithiocarbamate) salt is present in the reaction system. 5.The process according to claim 1, wherein the reaction is carried out inthe presence of 0.3 to 2.0 molar amount of a halogen ion to one molaramount of alkylenebis(dithiocarbamate) salt under the condition that 1.3to 3.0 molar amount of divalent copper ion to one molar amount ofalkylenebis(dithiocarbamate) salt is present in the reaction system. 6.The process according to claim 1, wherein the reaction is carried out ata temperature from 10* to 100* C.
 7. The process according to claim 1,wherein the reaction is carried out with cupric halide.
 8. The processaccording to claim 1, wherein the reaction is carried out with awater-soluble divalent copper salt other than cupric halide in thepresence of a halogen ion.
 9. The process according to claim 1, whereinthe reaction is carried out under an oxidative condition.
 10. Theprocess according to claim 9, wherein the reaction is carried out underaeration.
 11. The process according to claim 9, wherein the reaction iscarried out under an acidic condition.
 12. The process according toclaim 9, wherein the reaction is carried out in the presence of 0.3 to2.0 molar amount of a halogen ion to one molar amount ofalkylenebis(dithiocarbamate) salt under the condition that 1.3 to 3.0molar amount of divalent copper ion to one molar amount ofalkylenebis(dithiocarbamate) salt is present in the reaction system. 13.The process according to claim 9, wherein the reaction is carried out ata temperature from 10* to 100* C.
 14. The process according to claim 1,followed by treatment of the reaction product with an oxidizing agent.15. The process according to claim 14, wherein the reaction is carriedout under an acidic condition.
 16. The process according to claim 14,wherein the treatment is carried out at a temperature from 10* to 100*C.
 17. An fungicidally and bactericidally active substance havingalkylenebis(dithiocarbamate) moiety, divalent copper atom and a halogenatom, these being chemically bonded, in a molar ratio of 1 : X : Ywherein X aNd Y are respectively satisfying the following relationships:1<X < or = 3 and 0<Y < or = 2, which is obtained by reactingalkylenebis(dithiocarbamic acid) in a salt form with a water-solubledivalent copper salt in the presence of more than 0.1 molar amount of ahalogen ion to one molar amount of alkylenebis(dithiocarbamate) salt inan aqueous medium at a temperature from 10* to 100* C under thecondition that more than 1.1 molar amount of divalent copper ion to onemolar amount of alkylenebis(dithiocarbamate) salt is present in thereaction system, and recovering the precipitate from the reactionmixture.
 18. A composition for agricultural use containing thefungicidally and bactericidally active substance of claim 17 and aninert carrier.
 19. A fungicidally and bactericidally active substancewhich comprises the oxidation product of the substance according toclaim 17.